Two-rings-containing phenyl ester compound and anti-ferroelectric liquid crystal composition containing the same

ABSTRACT

A two-rings-containing phenyl ester compound of the following general formula (1), ##STR1## wherein R 1  is a linear alkyl group having 5 to 12 carbon atoms, R 2  is a linear alkyl group having 1 to 15 carbon atoms, X 1  and X 2  are both hydrogen atoms or one of X 1  and X 2  is a fluorine atom and the other is a hydrogen atom, Y 1  and Y 2  are both hydrogen atoms or one of Y 1  and Y 2  is a fluorine atom and the other is a hydrogen atom, and A 1  is a hydrogen atom, --CH 3  or --CF 3 , provided that when A 1  is a hydrogen atom or --CH 3 , p is 0 and that when A 1  is --CF 3 , p is t and q is an integer of 5 to 8, and an anti-ferroelectric liquid crystal composition containing at least one of two-rings-containing phenyl ester compounds of the above general formula (1) in claim 1 and either an anti-ferroelectric liquid crystal compound or a mixture of anti-ferroelectric liquid crystal compounds.

The present invention relates to a novel two-rings-containing phenyl ester compound, an anti-ferroelectric liquid crystal composition containing the above compound, and a liquid crystal display device for which the anti-ferroelectric liquid crystal is adapted.

A liquid crystal display device has been so far applied to various small-sized display devices owing to its low-voltage operability, low power consumption and small thickness of display portion. With recent broadening of application and use of liquid crystal display devices to/in an information and office automation-related machine and equipment field and a television field, there are rapidly rising demands for high-performance, large-sized liquid crystal display devices having display capacity and display quality over presently available CRT display devices.

However, so long as a present nematic liquid crystal is used, it is not at all easy to increase the size, and to decrease the cost, of even an active matrix driven liquid crystal display device that is used for a liquid crystal television nowaday, due to its complicated production process and low yield. Further, for a simple matrix driven STN liquid crystal display device, large capacity actuation is not necessarily easy, the response time has its limitation, and it is difficult to display an animation. Further, in a display device for which a nematic liquid crystal is adapted, its narrow viewing angle is recently a serious problem. Therefore it cannot be said at present that a nematic liquid crystal display device satisfies the above demands for a high-performance large-sized liquid crystal display device.

Under the circumstances, it is a liquid crystal display device using a ferroelectric liquid crystal that is attracting attention as a fast liquid crystal display device. It attracts attention that a surface stabilized ferroelectric liquid crystal (SSFLC) device disclosed by Clark and Lagerwall has a fast response speed and a wide viewing angle, and its switching characteristics has been studied in detail. A member of ferroelectric liquid crystals have been synthesized for optimizing various physical property constants. However, it has problems in that its threshold characteristic is insufficient, that its contrast is poor since its layer structure is a chevron structure, that no fast response is accomplished, that alignment control is difficult so that it is not easy to accomplish the bistability which is one of the greatest characteristics of SSFLC, and that alignment destroyed by mechanical impact is difficult to restore. It is required to overcome these problems for practical use.

In addition to this, the development of devices having switching mechanisms different from that of SSFLC are simultaneously under way. Switching of a liquid crystal substance having an anti-ferroelectric phase (to be referred to as "anti-ferroelectric liquid crystal substance" hereinafter) among tristable states is also one of these new switching mechanisms (Japanese Journal of Applied Physics, Vol. 27, pp. 1729, 1988).

An anti-ferroelectric liquid crystal device has three stable states. That is, they are two uniform states (Ur, Ul) and a third state, observed in an anti-ferroelectric device. Chandani et al have reported that this third state is an anti-ferroelectric phase (Japanese Journal of Applied Physics, vol. 28, pp. L1261, 1989, Japanese Journal of Applied Physics, vol. 28, pp. L1265, 1989).

The above switching among tristable states is the first characteristic of an anti-ferroelectric liquid crystal device. The second characteristic of the anti-ferroelectric liquid crystal device is that a distinct threshold value is present relative to a charged voltage. Further, it has a memory effect, which is the third characteristic of the anti-ferroelectric liquid crystal device. By utilizing these excellent characteristics, a liquid crystal display device having a fast response speed and an excellent contrast can be achieved.

The anti-ferroelectric liquid crystal has another great characteristic in that that its layer structure easily performs switching on the basis of an electric field (Japanese Journal of Applied Physics, Vol. 28, pp. L119, 1989, Japanese Journal of Applied Physics, vol. 29, pp. L111, 1990).

On the basis thereof, a liquid crystal display device free of defects and capable of self-restoring alignment can be produced, and a liquid crystal device having an excellent contrast can be achieved.

Further, it has been demonstrated that voltage gradation which is almost impossible for a ferroelectric liquid crystal is possible for an anti-ferroelectric liquid crystal, it is made possible to shift toward a full-color display, and the importance of an anti-ferroelectric liquid crystal is increasing (Preprints of No. 4 Ferroelectric Liquid Crystal International Symposium, page 77, 1993).

As described above, an anti-ferroelectric liquid crystal is gaining reliable dominance, while it is desired to further improve its response speed.

Anti-ferroelectric liquid crystals which have been so far proposed have a response speed sufficient for achieving display devices at a certain level. However, when an attempt is made to achieve a high-definition display device whose number of scanning lines is at least 800, its response speed is not yet sufficient, and it is required to increase the response speed. Further, the serious problem with a liquid crystal device in general is that the response speed greatly depends upon temperature. This problems is also a burden on an anti-ferroelectric liquid crystal device, and it is strongly desired to decrease its temperature dependency.

For an anti-ferroelectric liquid crystal, there are two switching operations, one from an anti-ferroelectric state to a ferroelectric state and the other from a ferroelectric state to an anti-ferroelectric state. The speeds of these two switching operations by voltage, i.e., response speed, are important factors for determining a display quality.

The response speed particularly from an anti-ferroelectric state to a ferroelectric state (to be referred to as "response speed I" hereinafter) is important since it is, for example, a writing speed per a scanning line-line in simple matrix driving so that it determines the number of scanning lines which constitute one picture. That is, as the response speed I increases, the number of scanning lines can be increased, so that a high-definition device can be achieved.

Further, concerning the response speed from a ferroelectric state to an anti-ferroelectric state (to be referred to as "response speed II" hereinafter), a required speed alters depending upon a design of a drive method of the device. For example, it alters by the set voltage of an offset voltage. However, when the response speed II is too high, no ferroelectric state can be fully maintained (a light or dark state cannot be maintained). When it is too low, disadvantageously, no change from a ferroelectric state to an anti-ferroelectric state takes place (no rewriting from a light or dark state to a dark or light state can be performed).

That is, in the response speed II, an optimum response speed is set after a drive method is determined.

As explained above, a fast response speed I is important for achieving a high-definition device.

Anti-ferroelectric liquid crystals which have been already proposed have response speeds sufficient for achieving display devices at certain levels. However, for achieving a high-definition display device having a large number of scanning lines, their response speeds are not yet sufficient and are required to be further increased.

The problem of an anti-ferroelectric liquid crystal is to further increase its response speed, particularly to increase its response speed on a low-temperature side, as described above. Further, it is desirable to broaden the temperature range of the anti-ferroelectric phase and have a smetic A phase on a high-temperature side.

M. Nakagawa has shown that the response speed of an anti-ferroelectric liquid crystal depends upon the rotation viscosity of liquid crystal molecules (Masahiro Nakagawa, Japanese Journal of Applied Physics, 30, 1759 (1991)). That is, with a decrease in viscosity, the response speed increases.

When the response speed relative to temperature is observed, the response speed starts to decrease around room temperature and exponential-functionally decreases in the temperature range lower than room temperature. An anti-ferroelectric liquid crystal has a high viscosity since its liquid crystal phase is a smetic phase, so that its viscosity sharply increases on a low-temperature side, and it is considered that the response speed sharply decreases due to the viscosity resistance thereof.

In one method for overcoming the above problem, an attempt is being made to develop an anti-ferroelectric liquid crystal having a low viscosity, while anti-ferroelectric liquid crystal having a proper tilt angle, a proper response speed and the temperature range of an anti-ferroelectric phase and having a low viscosity has been not actually developed.

In another method, a device is provided with a heater. This method can reliably overcome the problem, while this method cannot be said to be practically advantageous since the production of a display device requires an additional cost and since the transmission decreases due to the heater.

In further another method, it is conceivable to make an attempt to synthesize a compound having a relatively low viscosity and add the compound to a liquid crystal composition to decrease the viscosity of the composition as a whole so as to improve the response speed, and this method is considered the most practical solution at present.

A substance used in the above method is naturally one having a low molecular weight. However, when the molecular weight is too low, disadvantageously, the substance which is added volatilizes and dissipates with time and the transition temperature of the composition from an isotropic phase to a liquid crystal phase is too low.

It is generally considered that when an anti-ferroelectric liquid crystal device is used as a display, the device has a temperature of at least about 40° C. due to backlight.

For normal driving of the device, therefore, the upper-limit temperature of the anti-ferroelectric phase is required to be at least 40° C., preferably at least 50° C. And, desirably, a smetic A phase for obtaining excellent alignment is practically present on the high-temperature side of this temperature.

Further, on the low-temperature side, the device is at least required to be driven at 10° C. The lower-limit temperature of the anti-ferroelectric phase is at least required to be 0° C.

The present invention has been made from the above point of view, and has been arrived at by finding the following. When a novel two-rings-containing phenyl ester compound of the general formula (1), having the following specific structure, is incorporated into an anti-ferroelectric liquid crystal, an anti-ferroelectric phase can be secured in a broad temperature range, a smetic A phase can be also allowed to be present at the same time, and an anti-ferroelectric liquid crystal composition which shows highly fast response speed at a low temperature can be obtained.

That is, according to the present invention, there is provided a two-rings-containing phenyl ester compound of the following general formula (1), ##STR2## wherein R¹ is a linear alkyl group having 5 to 12 carbon atoms, R² is a linear alkyl group having 1 to 15 carbon atoms, X¹ and X² are both hydrogen atoms or one of X¹ and X² is a fluorine atom and the other is a hydrogen atom, Y¹ and Y² are both hydrogen atoms or one of Y¹ and Y² is a fluorine atom and the other is a hydrogen atom, and A¹ is a hydrogen atom, --CH₃ or --CF₃, provided that when A¹ is a hydrogen atom or --CH₃, p is 0 and that when A¹ is --CF₃, p is 1 and q is an integer of 5 to 8.

According to the present invention, further, there is provided an anti-ferroelectric liquid crystal composition prepared by incorporating the two-rings-containing phenyl ester compound of the general formula (1) into an anti-ferroelectric liquid crystal compound or a mixture of anti-ferroelectric liquid crystal compounds.

According to the present invention, furthermore, there is provided a simple matrix liquid crystal display device characterized in that an anti-ferroelectric liquid crystal composition containing the above two-rings-containing phenyl ester compound of the general formula (1) is held between one substrate having scanning electrodes disposed in a matrix form and the other substrate having signal electrodes disposed in a matrix form.

The two-rings-containing phenyl ester compound, the anti-ferroelectric liquid crystal composition and the simple matrix liquid crystal display device of the present invention will be explained further in detail hereinafter.

In the two-rings-containing phenyl ester compound of the general formula (1), the linear alkyl group as R¹ has 5 to 12 carbon atoms, preferably 8 to 12 carbon atoms. When a compound of the general formula (1) in which R¹ is a liner alkyl group having 7 carbon atoms or less, particularly 4 carbon atoms or less, is incorporated into an anti-ferroelectric liquid crystal or an anti-ferroelectric liquid crystal composition, there is a high effect on decreasing the viscosity and the response speed is greatly improved, while the tilt angle tends to be greatly decreased. When the number of carbon atoms is 13 or more, the compound of the general formula (1) shows a decreased effect on the response speed when incorporated into an anti-ferroelectric liquid crystal compound or a mixture of anti-ferroelectric liquid crystal compounds since the compound of the general formula (1) itself presumably has an increased viscosity.

When A¹ in the general formula (1) is a hydrogen atom, a compound of the general formula (1) in which p is 0 and R² is a linear alkyl group having 2 to 10 carbon atoms is preferred, and further, one which is the above compound and has a smetic A phase is further preferred. The substitution of fluorine atom on the phenyl group does not have any drastic effect. However, all of a compound of the general formula (1) in which X² is a fluorine atom and each of X¹, Y¹ and Y² is a hydrogen atom (Examples 27, 32) and a compound of the general formula (1) in which Y² is a fluorine atom and each of X¹, X² and Y¹ is a hydrogen atom (Examples 28-31) show a greater effect on the improvement of the response speed than that of any compound having no fluorine atom substituted.

In the two-rings-containing phenyl ester compound of the general formula (1), when A¹ is --CH₃ or --CF₃, the carbon atom to which A¹ bonds is an asymmetric atom, and it can be an optically active compound. In this case, the chiral source used in the chiral portion of the compound of the general formula (1) includes 2-alkanols such as 2-hexanol, and 2-hexanol, 2-octanol and 2-decanol are commercially easily available.

When A¹ is --CH₃, preferred is a compound of the general formula (1) in which p is 0 and R² is a linear alkyl group having 3 to 8 carbon atoms. The effect of fluorine substitution on phenyl group is not much drastic. However, depending upon position of the fluorine substitution, the effect of the incorporation is greater than that of a non-substituted optical active compound.

That is, all of an optically active compound in which one of X¹ and X² is a fluorine atom and both Y¹ and Y² are hydrogen atoms (Examples 8-14, 23-25), an optically active compound in which both X¹ and X² are hydrogen atoms and one of Y¹ and Y² is a fluorine atom (Examples 15, 16, 26) and an optically active compound in which one of X¹ and X² is a fluorine atom and one of Y¹ and Y² is a fluorine atom (Examples 17-20) show a greater effect on the improvement of response speed than a non-substituted optically active compound.

However, these compounds are likely to relatively decrease the tilt angle, and are limited in this aspect. The most desirable compound which shows a small decrease in tilt angle and a great improvement in response speed when A¹ is --CH₃ is an optically active compound in which X² is a fluorine atom and all of X¹, Y¹ and Y² are hydrogen atoms (Examples 8-13, 23-25).

A compound in which p is 1, q is 5 and R² is ethyl (n=2) when A¹ is --CF₃ is preferred (Examples 21, 22), and further, a compound in which all of X¹, X², Y¹ and Y² are hydrogen atoms is preferred (Example 21).

The present invention uses an anti-ferroelectric liquid crystal composition prepared by mixing at least one of two-rings-containing phenyl ester compounds of the general formula (1) with an anti-ferroelectric liquid crystal compound or a mixture of anti-ferroelectric liquid crystal compounds. The mixing ratio is selected such that the anti-ferroelectric liquid crystal composition at least has an anti-ferroelectric phase in the temperature range of from 0° C. to 40° C., preferably in the temperature range of from -20° C. to +50° C.

The mixing proportion is difficult to uniformly determine, since the effect thereof differs depending upon the kind of the two-rings-containing phenyl ester compound selected or the kind of the anti-ferroelectric liquid crystal, while the amount of the two-rings-containing phenyl ester compound of the general formula (1) based on the weight or molar amount of the anti-ferroelectric compound or the mixture of anti-ferroelectric compounds is 1 to 70%, preferably 5 to 60%, particularly 10 to 50%.

In practical use, it is preferred to form a composition having a smetic A phase on a temperature side higher than a temperature at which it shows an anti-ferroelectric phase. When no smetic A phase is presents, the alignment properties are greatly poor, and it is difficult to obtain a high contrast.

The anti-ferroelectric liquid crystal compound(s), with which the two-rings-containing phenyl ester compound of the general formula (1)in the present invention is mixed, is/are particularly preferably anti-ferroelectric liquid crystal(s) of the following general formula (2). ##STR3## wherein R³ is a linear alkyl group having 4 to 12 carbon atoms, R⁴ is a linear alkyl group having 1 to 12 carbon atoms, Z is a hydrogen atom or a fluorine atom, A² is a --CH₃ or --CF₃, is 0 or 1, t is an integer of 5 to 8, and C* is an asymmetric carbon, provided that when A² is --CH₃ and s is 0, R⁴ is a linear alkyl group having 3 to 10 carbon atoms, that when A² is --CF₃ and s is 0, R⁴ is a linear alkyl group having 4 to 8 carbon atoms, and that when A² is --CF₃ and s is 1, t is an integer of 5 to 8 and R⁴ is a linear alkyl group having 1 to 6 carbon atoms.

In the anti-ferroelectric liquid crystal compound of the general formula (2), R³ is preferably a linear alkyl group having 6 to 10 carbon atoms. When the number of carbon atoms is 5 or less, the temperature range of the anti-ferroelectric phase is narrow and the tilt angle is very small, so that the composition is not proper for practical use. When the number of carbon atoms exceeds 10, the viscosity of the composition of the general formula (2) itself is high, and it is therefore required to incorporate a large amount of the two-rings-containing phenyl ester compound, so that there arise other problems such as a decrease in tilt angle.

In the anti-ferroelectric liquid crystal compound of the general formula (2), preferred is an anti-ferroelectric liquid crystal compound in which A² is --CH₃, s is 0 and R⁴ is a linear alkyl group having 4, 6 or 8 carbon atoms. Further, a compound of which the phenyl group has a fluorine substituent (Z in the general formula (2)) is preferred since it exhibits an anti-ferroelectric phase in a broader temperature range.

An anti-ferroelectric liquid crystal compound in which A² is --CF₃, s is 0 and R⁴ is a linear alkyl group having 6 carbon atoms and an anti-ferroelectric liquid crystal compound in which A² is --CF₃, s is 1, t is 5 or 7 and R⁴ is ethyl are preferred.

Particularly preferably, the anti-ferroelectric liquid crystal composition of the present invention at least has an anti-ferroelectric phase in the temperature range of from 0° to 40° C. and at least has a smetic A phase on a temperature side higher than a temperature at which it exhibits an anti-ferroelectric phase.

The anti-ferroelectric liquid crystal composition of the present invention has an anti-ferroelectric phase in a broad temperature range and is improved in the response speed, particularly in the response speed, from an anti-ferroelectric state to a ferroelectric state, and can be used for an anti-ferroelectric liquid crystal display device which can be suitably actuated in a broader temperature range.

That is, in a simple matrix liquid crystal display device having the anti-ferroelectric liquid crystal composition of the present invention held between substrates having scanning electrodes and signal electrodes disposed in a matrix form, the actuation by voltage can be performed by switching between one anti-ferroelectric state and two ferroelectric states.

The optically active 2-alkanols used for the synthesis of the compound of the general formula (1) in the present invention can be selected from commercially available ones. Further, optically active 1,1,1-trifluoro-7-ethoxy-2-heptanol and 1,1,1-trifluoro-8-ethoxy-2-octanol can be prepared by the method already disclosed by the present inventors (Japanese Laid-open Patent Publication No. 983/1992).

The process for producing the two-rings-containing phenyl ester compound of the general formula (1), provided by the present invention, is outlined by the following reaction scheme. ##STR4##

In the above reaction scheme, Ph(F) is a 1,4-phenylene group which may have a fluorine atom substituted on its position 2 or 3, AcO is an acetyl group (CH₃ COO--), and R¹, A¹ and R² are as defined in the general formula (1).

The above production process will be briefly explained below.

(i) Ester (1) is prepared by reacting an aliphatic acid chloride with p-hydroxybenzoic acid which may have fluorine atom substituted on its ring.

(ii) The ester (1) is chlorinated with thionyl chloride.

(iii) Acetoxybenzoic acid is chlorinated with thionyl chloride.

(iv) Ester (4) is prepared by reacting the chloride in (3) with an alcohol (including an optically active alcohol).

(v) The ester (4) is deacetylated with benzylamine.

(vi) The chlorinated product (2) and the deacetylated product (5) are reacted.

Further, the anti-ferroelectric liquid crystal compound of the general formula (2) used for preparing the anti-ferroelectric liquid crystal composition in the present invention is produced by the following method. ##STR5##

In the above reaction scheme, AcO-- is a CH₃ COO-- group, Ph(F) is a 1,4-phenylene group which may be substituted with a fluorine atom on its 3-position (Z=H or F in the general formula (2), R⁴, R⁴ and A² are as defined in the general formula (2), C* is asymmetric carbon, and Ph is a phenyl group or a 1,4-phenylene group.

The above production method will be briefly explained below.

(a) p-Acetoxybenzoic acid substituted or non-substituted with fluorine is chlorinated with thionyl chloride.

(b) The chlorinated product (a) and an optically active alcohol are reacted to form an ester.

(c) The ester (b) is deacetylated.

(d) Alkyloxybiphenylcarboxylic acid is chlorinated.

(e) Phenol (c) which is a deacetylation product of ester and the chlorinated product (d) are reacted to form a liquid crystal.

The present invention provides a novel two-rings-containing phenyl ester compound. When incorporated as one component for an anti-ferroelectric liquid crystal composition, the novel two-rings-containing phenyl ester compound increases the response speed of the composition in a broad temperature range. On the other hand, the novel two-rings-containing phenyl ester compound hardly impairs other properties, so that there can be provided an anti-ferroelectric liquid crystal display device having a high display quality in a broad temperature range.

EXAMPLES

The present invention will be explained further in detail with reference to Examples hereinafter, while the present invention shall not be limited to these Examples.

EXAMPLE 1 R-4-(1-methylheptyloxycarbonyl)phenyl-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E1))

(1) Preparation of 4-undecanoyloxybenzoic acid

12.7 Grams (0.0917 mol) of p-hydroxybenzoic acid was added to 150 ml of dichloromethane, and to this suspension was added 10.2 g (0.0917 mol) of triethylamine. The mixture was stirred until a homogeneous solution was formed. 19.7 Grams (0.096 mol) of undecanoyl chloride was added to the solution at such a rate that the dichloromethane was not refluxed. Then, 1.0 g (0.0085 mol) of 4-dimethylaminopyridine was added, and the mixture was stirred at room temperature overnight. 1N Hydrochloric acid was added to the reaction mixture and the mixture was subjected to extraction with ether. The ether was distilled off, and the resultant crude product was washed with hexane.

The crude product was dried to give 20.6 g (yield 85%) of the intended carboxylic acid.

(2) Preparation of 4-acetoxy-1-(1-methylheptyloxycarbonyl)benzene

Thionyl chloride in an amount of 60 ml was added to 10.8 g (0.06 mol) of 4-acetoxybenzoic acid, and the mixture was allowed to react under reflux for 7 hours. Then, excessive thionyl chloride was distilled off, and then 10 ml of pyridine and 5.24 g (0.0402 mol) of R-2-octanol were dropwise added. After the addition, the mixture was stirred at room temperature for a whole day, then diluted with 200 ml of ether, and an organic layer was consecutively washed with diluted hydrochloric acid, with a 1N sodium hydroxide aqueous solution and with water, and dried over magnesium sulfate. The solvent was distilled off, and the resultant crude intended product was purified by silica gel column chromatography using hexane/ethyl acetate as a solvent, to give 10.6 g (yield 90%) of the intended product.

(3) Preparation of 4-hydroxy-1-(1-methylheptyloxycarbonyl)benzene

10.6 Grams (0.0361 mol) of the compound obtained in the above (2) was dissolved in 250 ml of ethanol, and 7.74 g (0.0772 mol) of benzylamine was dropwise added. Further, the mixture was stirred at room temperature for a whole day, then diluted with 300 ml of ether, consecutively washed with diluted hydrochloric acid and with water, and dried over magnesium sulfate. The solvent was distilled off, and the residue was subjected to silica gel column chromatography for isolation and purification, to give 8.9 g (0.0356 mol) of the intended product (yield 98%).

(4) Preparation of R-4-(1-methylheptyloxycarbonyl)phenyl-4-n-undecanoyloxybenzoate

Thionyl chloride in an amount of 15 ml was added to 3.1 mmol of the compound obtained in the above (1), and the mixture was refluxed under heat for 5 hours. Excessive thionyl chloride was distilled off, then 2 ml of pyridine and 2.12 mmol of the compound obtained in the above (3) were added, and the mixture was allowed to react at room temperature for 10 hours. After the completion of the reaction, the reaction mixture was diluted with 300 ml of ether, and consecutively washed with diluted hydrochloric acid, with a 1N sodium carbonate aqueous solution and with water, and an organic layer was dried over magnesium sulfate. Then, the solvent was distilled off, and the residue was subjected to silica gel column chromatography to isolate 0.99 g (0.00184 mol) of the end product (E1)(yield 87%).

The end product was measured for physical properties, etc., and the measurement results are shown below.

EXAMPLES 2 AND 3 Preparation of R-4-(1-methylpentyloxycarbonyl)phenyl-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₄ H₉ (E2)) and R-4-(1-methylnonyloxycarbonyl)phenyl-4-n-undecanonyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₈ H₁₇ (E3))

End products were obtained in the same manner as in Example 1 except that R-2-octanol was replaced with R-2-hexanol or R-2-decanol.

The results of measurement for physical properties, etc., are shown below.

The chemical formulae of the intended products obtained in Examples 1 to 3 are shown below.

Table 1 shows H-NMR data of these compounds, and Table 2 shows results of measurement of their phase sequences.

The physical properties, etc., described below were measured as follows.

Phase identification was carried out by texture observation and DSC (differential scanning calorimeter) measurement.

Response speed and tilt angle were measured as follows. A liquid crystal cell (cell thickness 1.8 μm) having a rubbing-treated polyimide thin film and ITO electrodes was charged with a liquid crystal in an isotropic state. The cell was gradually cooled at a rate of 1° C./minute to align the liquid crystal in an SA phase. The cell was placed between polarization plates crossing at right angles such that the layer direction of the liquid crystal was in parallel with an analyzer or a polarizer. A step voltage of 35 V at a frequency of 10 Hz was applied to the liquid crystal cell, and the liquid crystal cell was measured for a response speed. The time required for transmitted light change changing from 10 to 90% was defined as a response time. ##STR6##

                  TABLE 1                                                          ______________________________________                                         H-NMR data of E1-E3                                                            Hydrogen atom                                                                  number      1     2        3   4      5   6                                    ______________________________________                                         E1 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  E2 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  E3 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         Phase sequence (E1-E3)                                                         Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E1   I     (28)   SA   (22)  SCA*  (12) Cr                                     E2   I     (31)   SA   (22)  SCγ*                                                                           (18) SCA*  (<0) Cr                          E3   I     (21)   SA   (13.2)                                                                               SCA*  (13) Cr                                     ______________________________________                                          Notes to Table 2                                                               Parenthesized values = phase transition temperature (°C.). The          abbreviation in Table 2 are as follows.                                        I: isotropic phase,                                                            SA: smectic A phase,                                                           SCA*: antiferroelectric smectic C phase,                                       SIA*: antiferroelectric smectic I phase,                                       SCγ*: ferrielectric phase, Cr: crystal phase                       

EXAMPLES 4-7 Preparation of R-4-(1-methylheptyloxycarbonyl)phenyl-4-n-nonanoyloxybenzoate (Formula (1): R¹ =C₈ H₁₇, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E4)), R-4-(1-methylheptyloxycarbonyl)phenyl-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E5)), R-4-(1-methylheptyloxycarbonyl)-phenyl-4-n-dodecanoyloxybenzoate (Formula (1): R¹ =C₁₁ H₂₃, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E6)), and R-4-(1-methylheptyloxycarbonyl)phenyl-4-n-tridecanoyloxybenzoate (Formula (1): R¹ =C₁₂ H₂₅, A¹ =CH₃, X¹, X², Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E7))

The intended products were obtained in the same manner as in Example 1 except that the undecanoyl chloride in Example 1 was replaced with nonanoyl chloride, decanoyl chloride, dodecanoyl chloride or tridecanoyl chloride.

The results of measurement of physical properties, etc., are as follows. For abbreviations in Table 4, see notes to Table 2. ##STR7##

                  TABLE 3                                                          ______________________________________                                         H-NMR data of E4-E7                                                            Hydrogen atom                                                                  number      1     2        3   4      5   6                                    ______________________________________                                         E4 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  E5 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  E6 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  E7 (ppm)    2.6   7.3      8.3 7.2    8.1 5.2                                  ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                         Phase sequence (E4-E7)                                                         Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E4    I      (25)    Cr                                                        E5    I      (27)    SA   (10)   SCA*   (0)   Cr                               E6    I      (30)    SA   (29.5) Cr                                            E7    I      (35)    Cr                                                        ______________________________________                                    

EXAMPLE 8 Preparation of R-4-(1-methylheptyloxycarbonyl)phenyl-2-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X² =F, X¹, Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E8))

The intended product was synthesized in the same manner as in Example 1 except that the 4-undecanoyloxybenzoic acid in Example 1 was replaced with 2-fluoro-4-undecanoyloxybenoic acid.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2.

EXAMPLES 9 AND 10 Preparation of R-4-(1-methylpentyloxycarbonyl)phenyl-2-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X² =F, X¹, Y¹, Y² =H, p=0, R² =C₄ H₉ (E9)) and R-4-(1-methylnonyloxycarbonyl)phenyl-2-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X² =F, X¹, Y¹, Y² =H, p=0, R² =C₈ H₁₇ (E10))

The intended products were obtained in the same manner as in Example 8 except that the R-2-octanol in Example 8 was replaced with R-2-hexanol or R-2-decanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2. ##STR8##

                  TABLE 5                                                          ______________________________________                                         H-NMR data of E8-E10                                                           Hydrogen                                                                       atom number                                                                               1     2        3   4      5   6                                     ______________________________________                                         E8 (ppm)   2.6   7.1      8.2 7.2    8.1 5.2                                   E9 (ppm)   2.6   7.1      8.2 7.2    8.1 5.2                                   E10 (ppm)  2.6   7.1      8.1 7.3    8.1 5.2                                   ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                         Phase sequence (E8-E10)                                                        Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E8    I      (22)    SA      (0.8)                                                                              SCA*   (<0)  Cr                               E9    I      (22)    SA   (-12)  Cr                                            E10   I      (18)    SA   (8)    Cr                                            ______________________________________                                    

EXAMPLES 11-13 Preparation of R-4-(1-methylheptyloxycarbonyl)phenyl-2-fluoro-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, A¹ =CH₃, X² =F, X¹,Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E11)), R-4-(1-methylheptyloxycarbonyl)phenyl-2-fluoro-4-n-dodecanoyloxybenzoate (Formula (1): R¹ =C₁₁ H₂₃, A¹ =CH₃, X² =F, X¹, Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E12)), and R-4-(1-methylheptyloxycarbonyl)phenyl-2-fluoro-4-n-tridecanoyloxybenzoate (Formula (1): R¹ =C₁₂ H₂₅, A¹ =CH₃, X² =F, X¹, Y¹, Y² =H, p=0, R² =C₆ H₁₃ (E13))

The intended products were obtained in the same manner as in Example 8 except that the 2-fluoro-4-undecanoyloxybenzoic acid in Example 8 was replaced with 2-fluoro-4-decanoyloxybenzoic acid (Example 11), 2-fluoro-4-dodecanoyloxybenzoic acid (Example 12) or 2-fluoro-4-tridecanoyloxybenzoic acid (Example 13).

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2. ##STR9##

                  TABLE 7                                                          ______________________________________                                         H-NMR data of E11-E13                                                          Hydrogen atom                                                                  number      1     2        3   4      5   6                                    ______________________________________                                         E11 (ppm)   2.6   7.1      8.2 7.3    8.1 5.2                                  E12 (ppm)   2.6   7.1      8.2 7.3    8.1 5.2                                  E13 (ppm)   2.6   7.1      8.2 7.3    8.1 5.2                                  ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                         Phase sequence (E11-E13)                                                       Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E11   I      (20)    SA    (-29) Cr                                            E12   I      (25)    SA      (15)                                                                               SCA*   (13)  Cr                               E13   I      (23)    SA      (21)                                                                               Cr                                            ______________________________________                                    

EXAMPLE 14 Preparation of R-4-(1-methylnonyloxycarbonyl)phenyl-3-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X¹ =F, X², Y¹, Y² =H, p=0, R² =C₈ H₁₇ (E14))

The intended product was obtained in the same manner as in Example 1 except that the 4-undecanoyloxybenzoic acid was replaced with 3-fluoro-4-undecanoyloxybenzoic acid and that the 2-octanol was replaced with 2-decanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2.

EXAMPLE 15 Preparation of R-3-fluoro-4-(1-methylnonyloxycarbonyl)phenyl-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, Y² =F, X¹, X², Y¹ =H, p=0, R² =C₈ H₁₇ (E15))

The intended product was obtained in the same manner as in Example 1 except that the 4-acetoxybenzoic acid was replaced with 2-fluoro-4-acetoxybenzoic acid and that the 2-octanol was replaced with 2-decanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2.

EXAMPLE 16 Preparation of R-2-fluoro-4-(1-methylnonyloxycarbonyl)phenyl-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, Y¹ =F, X¹, X², Y² =H, p=0, R² =C₈ H₁₇ (E16))

The intended product was obtained in the same manner as in Example 1 except that the 4-acetoxybenzoic acid was replaced with 3-fluoro-4-acetoxybenzoic acid and that the 2-octanol was replaced with 2-decanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2. ##STR10##

                  TABLE 9                                                          ______________________________________                                         H-NMR data of E14-E16                                                          Hydrogen                                                                       atom number                                                                              1       2     3     4   5      6   7                                 ______________________________________                                         E14 (ppm) 2.6     7.3   8.0   8.0 7.3    8.2 5.2                               E15 (ppm) 2.6     7.3   8.2   7.1 7.1    8.0 5.2                               E16 (ppm) 2.6     7.2   8.3   7.3 7.9    5.2 --                                ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                         Phase sequence (E14-E16)                                                       Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E14   I       (5)    Cr                                                        E15   I      (24)    SA    (22)  SCA*   (8)  Cr                                E16   I       (3)    Cr                                                        ______________________________________                                    

EXAMPLES 17-20 Preparation of R-2-fluoro-4-(1-methylnonyloxycarbonyl)phenyl-3-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X¹, Y¹ =F, X², Y² =H, p=0, R² =C₈ H₁₇ (E17)), R-2-fluoro-4-(1-methylnonyloxycarbonyl)phenyl-2-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X², Y¹ =F, X¹, Y² =H, p=0, R² =C₈ H₁₇ (E18)), R-3-fluoro-4-(1-methylnonyloxycarbonyl)phenyl-3-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X¹, Y² =F, X², Y¹ =H, p=0, R² =C₈ H₁₇ (E19)), and R-3-fluoro-4-(1-methylnonyloxycarbonyl)phenyl-2-fluoro-4-n-undecanoyloxybenzoate (Formula (1): R¹ =C₁₀ H₂₁, A¹ =CH₃, X², Y² =F, X¹, Y¹ =H, p=0, R² =C₈ H₁₇ (E20))

The intended products were obtained in the same manner as in Example 1 except that the 4-acetoxybenozic acid was replaced with 2-fluoro-4-acetoxybenzoic acid and 3-fluoro-4-acetoxybenozic acid, that the p-hydroxybenzoic acid was replaced with 3-fluoro-4-hydroxybenzoic acid and 2-fluoro-4-hydroxybenzoic acid and that the 2-octanol was replaced with 2-decanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2.

                  TABLE 11                                                         ______________________________________                                         H-NMR data of E17-E20                                                          Hydrogen                                                                       atom number                                                                               1     2        3   4      5   6                                     ______________________________________                                         E17 (ppm)  2.6   7.3      8.1 7.3    8.0 5.2                                   E18 (ppm)  2.6   7.1      8.2 7.4    7.9 5.2                                   E19 (ppm)  2.6   7.3      8.0 7.1    8.0 5.2                                   E20 (ppm)  2.6   7.0      8.1 7.1    8.0 5.2                                   ______________________________________                                    

                  TABLE 11                                                         ______________________________________                                         H-NMR data of E17-E20                                                          Hydrogen                                                                       atom number                                                                               1     2        3   4      5   6                                     ______________________________________                                         E17 (ppm)  2.6   7.3      8.1 7.3    8.0 5.2                                   E18 (ppm)  2.6   7.1      8.2 7.4    7.9 5.2                                   E19 (ppm)  2.6   7.3      8.0 7.1    8.0 5.2                                   E20 (ppm)  2.6   7.0      8.1 7.1    8.0 5.2                                   ______________________________________                                    

                  TABLE 12                                                         ______________________________________                                         Phase sequence (E17-E20)                                                       Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E17     I      (-14)   Cr                                                      E18     I         (6)  Cr                                                      E19     I         (1)  SA   (-7) Cr                                            E20     I        (19)  SA   (13) SCA*   (1)  Cr                                ______________________________________                                    

EXAMPLE 21 Preparation of R-4-(1-trifluoromethyl-6-ethoxyhexyloxycarbonyl)phenyl-4-n-undecanoyloxybenzoate (Formula (1): C₁₀ H₂₁, A¹ =CF₃, X¹, X², Y¹, Y² =H, p=1, q=5, R² =C₂ H₅ (E21))

An optically active compound was obtained in the same manner as in Example 1 except that the 2-octanol was replaced with 1,1,1-trifluoro-7-ethoxy-2-heptanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2.

EXAMPLE 22 Preparation of R-4-(1-trifluoromethyl-6-ethoxyhexyloxycarbonyl)phenyl-2-fluoro-4-n-undecanoyloxybenzoate (Formula (1): C₁₀ H₂₁, A¹ =CF₃, X² =F, X¹, Y¹, Y² =H, p=1, q=5, R² =C₂ H₅ (E22))

An optically active compound was obtained in the same manner as in Example 8 except that the 2-octanol was replaced with 1,1,1-trifluoro-7-ethoxy-2-heptanol.

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2. ##STR11##

                  TABLE 13                                                         ______________________________________                                         H-NMR data of E21 and E22                                                      Hydrogen                                                                       atom number                                                                             1     2       3   4     5   6     7   8                               ______________________________________                                         E21 (ppm)                                                                               2.6   7.3     8.2 7.2   8.1 5.6   3.4 1.2                             E22 (ppm)                                                                               2.6   7.1     8.2 7.4   8.2 5.6   3.4 1.2                             ______________________________________                                    

                  TABLE 14                                                         ______________________________________                                         Phase sequence (E21 and E22)                                                   Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E21      I              (-19)  Cr                                              E22      I              (-31)  Cr                                              ______________________________________                                    

EXAMPLES 23-26 Preparation of R-4-(1-methylbutyloxycarbonyl)phenyl-2-fluoro-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, X² =F, X¹, Y¹, Y² =H, p=0, A¹ =CH₃, R² =C₃ H₇ (E23)), R-4-(1-methylpentyloxycarbonyl)phenyl-2-fluoro-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, X² =F, X¹, Y¹, Y² =H, p=0, A¹ =CH₃, R² =C₄ H₉ (E24)), R-4-(1-methylhexyloxycarbonyl)henyl-2-fluoro-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, X² =F, X¹, Y¹, Y² =H, p=0, A¹ =CH₂, R² =C₅ H₁₁ (E25)), and R-4-(1-methyloctyloxycarbonyl)phenyl-2-fluoro-decanoyloxybenzoate (Formula (1): C₉ H₁₉, Y² =F, X¹, X², Y¹ =H, p=0, A¹ =CH₃, R² =C₇ H₁₅ (E26))

The intended products were obtained in the same manner as in Example 1 except that the 4-undecanoyloxybenzoic acid was replaced with 2-fluoro-4-decanoyloxybenzoic acid (Examples 23-25) or 4-decanoyloxybenzoic acid (Example 26) and that the 4-hydroxy-1-(1-methylheptyloxycarbonyl)benzene was replaced with 4-hydroxy-1-(1-methylbutyloxycarbonyl)benzene (Example 23), 4-hydroxy-1-(1-methylpentyloxycarbonyl)benzene (Example 24), 4-hydroxy-1-(1-methylhexyloxycarbonyl)benzene (Example 25), or 4-hydroxy-1-(1-methyloctyloxycarbonyl)benzene (Example 26).

The results of measurement of physical properties, etc., are as follows. For abbreviations, see notes to Tables 1 and 2. ##STR12##

                  TABLE 15                                                         ______________________________________                                         H-NMR data of E23-E26                                                          Hydrogen                                                                       atom number                                                                              1       2     3     4   5     6   7                                  ______________________________________                                         E23 (ppm) 2.6     7.0   7.0   8.2 7.3   8.2 5.2                                E24 (ppm) 2.6     7.1   7.1   8.1 7.3   8.1 5.2                                E25 (ppm) 2.6     7.1   7.1   8.2 7.3   8.2 5.2                                E26 (ppm) 2.6     7.3   8.2   7.1 7.1   8.0 5.3                                ______________________________________                                    

                  TABLE 16                                                         ______________________________________                                         Phase sequence (E23-E26)                                                       Phase sequence (parenthesized values =                                         transition temperature (°C.))                                           ______________________________________                                         E23   I      (27)    SA    (1)  SCA*   (-12) Cr                                E24   I      (25)    SA    (-12)                                                                               SCAγ*                                                                           (-14) Cr                                E25   I      (21)    SA    (-3) SCA*   (-18) Cr                                E26   I      (26)    SA    (22) SCA*    (-8) Cr                                ______________________________________                                    

EXAMPLE 27 Preparation of 4-heptyloxycarbonylphenyl-2-fluoro-4-n-decanonyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, X² =F, X¹, Y¹, Y² =H, A¹ =H, p=0, R² =C₆ H₁₃ (E27))

(1) Preparation of 4-decanoyloxy-2-fluorobenzoic acid

15.6 Grams (0.1 mol) of 4-hydroxy-2-fluorobenzoic acid was dissolved in 140 ml of dichloromethane. To the mixture were consecutively added 16 ml of triethylamine, 0.1 g (0.11 mol) of n-decanoic acid chloride and 0.97 (0.0079 mol) of dimethylaminopyridine, and the mixture was stirred at room temperature for a whole day. 10% Hydrochloric acid in an amount of 50 ml was added, and the mixture was subjected to extraction with 100 ml of ether three times. The organic layer was washed with a sodium chloride aqueous solution three times and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was washed with 400 ml of hexane to give 25.5 g of the intended product.

(2) Preparation of 4-acetoxy-1-heptyloxycarbonylbenzene

3.5 Grams of 4-acetoxybenzoic acid was added to 25 ml of thionyl chloride, and the mixture was allowed to react under reflux for 10 hours. Then, excessive thionyl chloride was distilled off, 10 ml of pyridine and 50 ml of toluene were then added, and 1.5 g of n-heptanol was dropwise added. After the addition, the mixture was refluxed under heat for 4 hours, and then the reaction mixture was allowed to cool and diluted with 500 ml of dichloromethane. An organic layer was consecutively washed with diluted hydrochloric acid, with a 1N sodium hydroxide aqueous solution and with water, and dried over magnesium sulfate. Further, the solvent was distilled off to give 1.7 g of the crude intended product.

(3) Preparation of 4-hydroxy-1-heptyloxycarbonylbenzene

1.7 Grams of the crude product obtained in (2) was dissolved in 50 ml of ethanol, and 4 g of benzylamine was dropwise added. Further, the mixture was stirred at room temperature for 4 hours, then diluted with 500 ml of chloroform, consecutively washed with diluted hydrochloric acid and with water, and dried over magnesium sulfate. The solvent was distilled off, and the product was isolated and purified by silica gel column chromatography to give 0.9 g of the intended product.

(4) Preparation of 4-heptyloxycarbonylphenyl-2-fluoro-4-n-decanonyloxybenzoate

(1) Thionyl chloride in an amount of 10 ml was added to 0.5 g (0.0017 mol) of the 4-decanoyloxybenzoic acid obtained in (1), and the mixture was refluxed under heat for 4 hours. The thionyl chloride was distilled off, and the resultant acid chloride was dissolved in 0.52 g of toluene. To the mixture were consecutively added 0.35 g (0.0015 mol) of the 4-hydroxy-1-heptyloxycarbonylbenzene obtained in (3) and 0.27 g (0.0034 mol) of pyridine, and the mixture was stirred at room temperature for 24 hours. Water in an mount of 10 ml was added, the mixture was stirred for 30 minutes, 20 ml of 1N hydrochloric acid was added, and the mixture was extracted with 20 ml of dichloromethane twice. An organic layer was washed with 20 ml of water, and dried over anhydrous sodium sulfate. The solvent was distilled off to give 0.60 g of a crude product. The crude product was purified by silica gel column chromatography to give 0.43 g of the intended product (to be referred to as "E27" hereinafter).

Table 17 shows the NMR data of the so-obtained intended product and the result of crystal phase identification thereof.

EXAMPLE 28 Preparation of 3-fluoro-4-heptyloxycarbonylphenyl-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, Y² =F, X¹, X², Y¹ =H, A¹ =H, p=0, R² =C₆ H₁₃ (E28))

The intended product (to be referred to as "E28" hereinafter) was obtained in the same manner as in Example 27 except that the 4-hydroxy-2-fluorobenzoic acid and the p-acetoxybenzoic acid were replaced with 4-hydroxybenzoic acid and 2-fluoro-4-acetoxybenzoic acid.

Table 17 shows the NMR data of the so-obtained intended product and the result of crystal phase identification thereof.

EXAMPLES 29-33 Preparation of 3-fluoro-4-undecyloxycarbonylphenyl-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, Y² =F, X¹, X², Y¹ =H, A¹ =H, p=0, R² =C₁₀ H₂₁ (E29)), 3-fluoro-4-nonyloxycarbonylphenyl-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, Y² =F, X¹, X², Y¹ =H, A¹ =H, p=0, R² =C₈ H₁₇ (E30)), 3-fluoro-4-propyloxycarbonylphenyl-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, Y² =F, X¹, X², Y¹ =H, A¹ =H, p=0, R² =C₂ H₅ (E31)), 4-nonyloxycarbonylphenyl-2-fluoro-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, X² =F, X¹, Y¹, Y² =H, A¹ =H, p=0, R² =C₈ H₁₇ (E32)) and 4-nonyloxycarbonylphenyl-4-n-decanoyloxybenzoate (Formula (1): R¹ =C₉ H₁₉, X¹ -Y² ==H, A¹ =H, p=0, R² =C₈ H₁₇ (E33))

The above compounds (E29-E33) were synthesized according to Example 27.

Table 17 shows the NMR data of the intended product and the result of crystal phase identification thereof. ##STR13##

                  TABLE 17                                                         ______________________________________                                         Hydrogen atom number of the                                                    formulae (ppm)                                                                 1      2      3     4   5    6   7   Phase sequence                            ______________________________________                                         E27  2.6   7      7   8.2 7.3  8.1 4.4 I   (61) SA  (33)                                                    Cr                                                                             E28 2.6 7.2 8.2 7.1 7.1 8 4.4 I (71) SA (37)                                   Cr                                                                             E29 2.6 7.3 8.2 7.1 7.1 8 4.4 I (70) SA (37)                                   Cr                                                                             E30 2.6 7.3 8.2 7.1 7.1 8 4.4 I (71) SA (37)                                   Cr                                                                             E31 2.6 7.3 8.2 7.1 7.1 8 4.4 I (77) SA (44)                                   Cr                                                                             E32 2.6 7.0 7.0 8.2 7.3 8.1 4.4 I (68) SA (42                                  ) Cr                                                                           E33 2.6 7.3 8.3 7.3 8.1 4.4 -- I (77) SA (37)                                   Cr                                               ______________________________________                                    

EXAMPLES 34-36

The above-obtained optically active compound E1, E2 or E3 in an amount of 30 wt. % was added to the following anti-ferroelectric liquid crystal A (to be referred to as AF1 hereinafter), and each of the resultant compositions was measured for a phase sequence, a response speed, a tilt angle, etc. Tables 18 and 19 show the results.

    AF1: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CH.sub.3)C.sub.6 H.sub.13

In the above formula, Ph is a 1,4-phenylene group, Ph(3F) is a 1,4-phenylene group substituted with F on its 3 position (Z=F in formula (2)), and C* is asymmetric carbon.

Each composition were measured for physical properties, etc., as follows.

Phase identification was carried out by texture observation and DSC (differential scanning calorimeter) measurement. The response speed and the tilt angle were measured as follows. A liquid crystal cell (cell thickness 1.8 μm) having a rubbing-treated polyimide thin film and ITO electrodes was charged with a composition in an isotropic state. The cell was gradually cooled at a rate of 1° C./minute to align the liquid crystal in an SA phase. The cell was placed between polarization plates crossing at right angles such that the layer direction of the liquid crystal was in parallel with an analyzer or a polarizer. A step voltage of 35 V at a frequency of 10 Hz was applied to the liquid crystal cell, and the liquid crystal cell was measured for a response speed. The time required for transmitted light change changing from 10 to 90% was defined as a response time.

The cell was rotated by applying a triangular voltage of 0.2 Hz±40 V, and the tilt angle was determined on the basis of its rotation angle.

EXAMPLES 37-40

The optically active compounds E4 to E7 obtained in Examples 4 to 7, in an amount of 30 wt. % each, were respectively added to AF1, and each of the resultant compositions was measured for a phase sequence, a response speed, a tilt angle, etc., in the same manner as in Example 35. Tables 18 and 19 show the results.

Parenthesized values in Table 18 show temperatures (°C.) of phase transition. Abbreviations stand for the following.

I: isotropic phase,

SA: smectic A phase,

SCA*: anti-ferroelectric smectic C phase,

SIA*: anti-ferroelectric smectic I phase,

SCV*: ferridielectric phase,

Cr: crystal phase

                                      TABLE 18                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                       Com- Weight                                      transition temperature (°C.))                                                                         ponent                                                                              ratio                                       __________________________________________________________________________     Liquid                                                                             I (140)                                                                             SA                                                                               (121)                                                                              SCA*                                                                               (20)                                                                              SIA*                                                                              (<0)                                                                              Cr                                                 crystal                                                                        AF1                                                                            Ex. 34                                                                             I (104)                                                                             SA                                                                               (79)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E1 =                                                                            70/30                                       Ex. 35                                                                             I (106)                                                                             SA                                                                               (79)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E2 =                                                                            70/30                                       Ex. 36                                                                             I (105)                                                                             SA                                                                               (79)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E3 =                                                                            70/30                                       Ex 37                                                                              I (100)                                                                             SA                                                                               (69)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E4 =                                                                            70/30                                       Ex. 38                                                                             I (106)                                                                             SA                                                                               (79)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E5 =                                                                            70/30                                       Ex. 39                                                                             I (106)                                                                             SA                                                                               (81)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E6 =                                                                            70/30                                       Ex. 40                                                                             I (104)                                                                             SA                                                                               (80)                                                                               SCA*                                                                               (<0)                                                                              Cr      AF1/E7 =                                                                            70/30                                       __________________________________________________________________________

                                      TABLE 19                                     __________________________________________________________________________     Measured                                                                              Response speed I                                                                           Response speed II                                                                        Tilt angle                                        temp. (°C.)                                                                    60  40  20  60 40  20 60 40 20                                          __________________________________________________________________________     Liquid crystal                                                                        854 1305                                                                               1935                                                                               611                                                                               2145                                                                               7885                                                                              29.9                                                                              29.4                                                                              28                                          AF1                                                                            Ex. 34 10   69 223 378                                                                               1300                                                                               6910                                                                              26 27 27                                          Ex. 35 16  215 732 147                                                                                690                                                                               2950                                                                              24 26 26                                          Ex. 36  7   27 115 241                                                                                360                                                                               1950                                                                              25 26 26                                          Ex. 37  5   14  75 130                                                                                484                                                                               2780                                                                              20 23 24                                          Ex. 38  7   31 177 282                                                                               1000                                                                               6910                                                                              24 26 26                                          Ex. 39 22  123 252 450                                                                               1360                                                                               8190                                                                              26 28 28                                          Ex. 40 34  185 418 468                                                                               1710                                                                               5340                                                                              27 28 29                                          __________________________________________________________________________      Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μ second.                                                       Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μ second.                                                 

In Table 18, the anti-ferroelectric phase of the liquid crystal AF1 is in the temperature range of from 121° C.-20° C., and the lower-limit temperature of the anti-ferroelectric phase of this liquid crystal is as high as 20° C., so that it can be actuated only at a temperature of at least 20° C. In contrast, each of the liquid crystal compositions containing 30 wt. % of the optically active compounds E1 to E7 has a lower-limit temperature of 0° C. or lower, and shows the temperature range of anti-ferroelectric phase preferred as a display device.

Further, in the response speed I from an anti-ferroelectric state to a ferroelectric state, the liquid crystal AF1 shows a low response speed and has a problem in practical use. On the other hand, the anti-ferroelectric liquid crystal compositions obtained by incorporating 30 wt. % of the optically active compounds E1 to E7 into the liquid crystal AF1 have greatly increased response speeds I and can be practically used, but the optically active compound E4 shows a relatively strong negative effect on decreasing the tilt angle.

EXAMPLES 41-46

The optically active compounds E8 to E13 obtained in Examples 8 to 13, in an amount of 30 wt. % each, were respectively added to AF1, and each of the resultant compositions was measured for a phase sequence, a response speed, a tilt angle, etc., in the same manner. Tables 20 and 21 show the results.

                                      TABLE 20                                     __________________________________________________________________________     Liquid                                                                             Phase sequence (parenthesized values =                                                                Com-  Weight                                        crystal                                                                            transition temperature (°C.))                                                                  ponent                                                                               ratio                                         __________________________________________________________________________     Ex. 41                                                                             I  (108)                                                                             SA (81)                                                                              SCA* (<0)                                                                              Cr AF1/E8 =                                                                             70/30                                         Ex. 42                                                                             I  (106)                                                                             SA (72)                                                                              SCA* (<0)                                                                              Cr AF1/E9 =                                                                             70/30                                         Ex. 43                                                                             I  (100)                                                                             SA (66)                                                                              SCA* (<0)                                                                              Cr AF1/E10 =                                                                            70/30                                         Ex. 44                                                                             I   (94)                                                                             SA (63)                                                                              SCA* (<0)                                                                              Cr AF1/E11 =                                                                            70/30                                         Ex. 45                                                                             I   (99)                                                                             SA (70)                                                                              SCA* (<0)                                                                              Cr AF1/E12 =                                                                            70/30                                         Ex. 46                                                                             I   (99)                                                                             SA (71)                                                                              SCA* (<0)                                                                              Cr AF1/E13 =                                                                            70/30                                         __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                                      TABLE 21                                     __________________________________________________________________________     Measured                                                                              Response speed I                                                                           Response speed II                                                                        Tilt angle                                        temp. (°C.)                                                                    60  40  20  60 40  20 60 40 20                                          __________________________________________________________________________     Liquid crystal                                                                        854 1305                                                                               1935                                                                               611                                                                               2145                                                                               7885                                                                              29.9                                                                              29.4                                                                              28                                          AF1                                                                            Ex. 41 8   40  140 281                                                                               922 5440                                                                              25 27 27                                          Ex. 42 6   53  307 120                                                                               431 2740                                                                              20 24 25                                          Ex. 43 6   13   54 138                                                                               657 1760                                                                              19 24 25                                          Ex. 44     11   43    665 2900  22 23                                          Ex. 45 5   35      447                                                                               1560   23 26 27                                          Ex. 46 6   26      540                                                                               1120   23 27 27                                          __________________________________________________________________________      Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μ second.                                                       Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μ second.                                                       Example 45: The upperlimit temperature of SCA* was so low that the             measurement at 60° C. was not carried out.                              Examples 46 and 47: The alignment state was defective so that the              measurement at 20° C. was not carried out.                        

As is clearly shown in Table 21, the optically active compounds E8 to E13 show remarkable effects on the improvement of the anti-ferroelectric liquid crystal in response speed, particularly on the improvement in the response speed from an anti-ferroelectric state to a ferroelectric state, but the compound E10 shows a somewhat strong negative effect on decreasing the tilt angle.

EXAMPLES 47 AND 48

The optically active compounds E14 and E16 obtained in Examples 14 and 16, in an amount of 30 wt. % each, were respectively added to AF1, and each of the resultant compositions was measured for a phase sequence, a response speed, a tilt angle, etc., in the same manner. Tables 22 and 23 show the results.

As is clearly shown in Table 23, the optically active compounds E14 and E16 show remarkable effects on the improvement of the anti-ferroelectric liquid crystal in response speed, particularly on the improvement in the response speed from an anti-ferroelectric state to a ferroelectric state, but these compounds show a somewhat strong negative effect on decreasing the tilt angle.

REFERENTIAL EXAMPLE 1

The optically active compound E15 obtained in Example 15, in an amount of 30 wt. %, was added to a liquid crystal AF1, and the mixture was measured for a phase sequence, a response speed, a tilt angle, etc. Tables 22 and 23 show the results.

The response speed on the low-temperature side is low instead of being increased.

                                      TABLE 22                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                       Com-  Weight                                     transition temperature (°C.))                                                                         ponent                                                                               ratio                                      __________________________________________________________________________     E47                                                                               I (95)                                                                               SA                                                                               (64)                                                                              SCγ*                                                                         (59)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E14 =                                                                            70/30                                      E48                                                                               I (98)                                                                               SA                                                                               (60)                                                                              SCA*                                                                               (<0)                                                                              Cr       AF1/E16 =                                                                            70/30                                      Ref.                                                                              I (105)                                                                              SA                                                                               (79)                                                                              SCγ*                                                                         (77)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E15 =                                                                            70/30                                      Ex. 1                                                                          __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 23                                                         ______________________________________                                         Measured                                                                               Response speed I                                                                            Response speed II                                                                           Tilt angle                                   temp. (°C.)                                                                     60    40     20    60   40   20   60  40   20                          ______________________________________                                         E47            9     36         887  2140     20   22                          E48           12     52         949  4890     21   23                          Ref. Ex. 1                                                                             34    526    4350  266  824  3230 26  28   28                          ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                        Examples 47 and 48: The upperlimit temperature of SCA* was low so that th      measurement at 60° C. was not carried out.                        

EXAMPLES 49-52

The optically active compounds E17 to E20 obtained in Examples 17 to 20, in an amount of 30 wt. % each, were respectively added to a liquid crystal AF1, and each of the resultant compositions was measured for a phase sequence, a response speed, a tilt angle, etc., in the same manner as in Example 34. Tables 24 and 25 show the results.

As shown in Table 25, the optically active compounds E17 to E20 show remarkable effects on the improvement of the anti-ferroelectric liquid crystal in response speed, particularly on the improvement in the response speed from an anti-ferroelectric state to a ferroelectric state, but the optically active compounds E17 to E19 also show a negative effect on decreasing the tilt angle.

                                      TABLE 24                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                       Com-  Weight                                     transition temperature (°C.))                                                                         ponent                                                                               ratio                                      __________________________________________________________________________     E49                                                                               I (89)                                                                               SA                                                                               (82)                                                                              SCγ*                                                                         (78)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E17 =                                                                            70/30                                      E50                                                                               I (97)                                                                               SA                                                                               (67)                                                                              SCγ*                                                                         (62)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E18 =                                                                            70/30                                      E51                                                                               I (91)                                                                               SA                                                                               (69)                                                                              SCγ*                                                                         (66)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E19 =                                                                            70/30                                      E52                                                                               I (100 )                                                                             SA                                                                               (70)                                                                              SCγ*                                                                         (67)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E20 =                                                                            70/30                                      __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 25                                                         ______________________________________                                         Measured                                                                               Response speed I                                                                            Response speed II                                                                           Tilt angle                                   temp. (°C.)                                                                     60    40     20    60   40   20   60  40   20                          ______________________________________                                         E49           14                2260          21   21                          E50            9     44         1035 5150     19   22                          E51           13     76          581 1790     21   23                          E52     6     154    1560  236   595 2025 22  26   27                          ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                        Examples 49: Due to defective alignment, only the response speed at            40° C. was measured.                                                    Example 50 and 51: The upperlimit temperature of SCA* was low so that the      measurement at 60° C. was not carried out.                        

EXAMPLES 53 AND 54

The optically active compound E1 obtained in Example 1, in an amount of 10 wt. % or 50 wt. %, was added to an anti-ferroelectric liquid crystal AF1, and each of the resultant compositions was measured for a phase sequence, a response speed, a tilt angle, etc., in the same manner. Tables 26 and 27 show the results.

EXAMPLE 55

The optically active compound E21 obtained in Example 21, in an amount of 10 wt. % or 50 wt. %, was added to an anti-ferroelectric liquid crystal AF1, and the resultant compositions were evaluated for its effects. The composition containing 30 wt. % of the compound E21 had an isotropic phase down to room temperature or lower, and its physical properties were unmeasurable.

Tables 26 and 27 show the physical property values of the composition containing 10 wt. % of the compound E21, as Example 55.

REFERENTIAL EXAMPLE 2

The optically active compound E22 obtained in Example 22, in an amount of 10 wt. % was added to an anti-ferroelectric liquid crystal AF1. However, the composition had an isotropic phase down to room temperature or lower, and its physical properties were unmeasurable.

                                      TABLE 26                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                      Com-  Weight                                      transition temperature (°C.))                                                                        ponent                                                                               ratio                                       __________________________________________________________________________     E53                                                                               I (126)                                                                             SA                                                                               (107)                                                                             SCγ*                                                                        (105)                                                                              SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E1 =                                                                             90/10                                       E54                                                                               I  (87)                                                                             SA                                                                                (60)                                                                             SCγ*                                                                        (58)                                                                               SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E1 =                                                                             50/50                                       E55                                                                               I (102)                                                                             SA                                                                               (101)                                                                             SCγ*                                                                        (99)                                                                               SCA*                                                                               (<0)                                                                              Cr                                                                               AF1/E21 =                                                                            90/10                                       __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 27                                                         ______________________________________                                         Measured                                                                               Response speed I                                                                            Response speed II                                                                           Tilt angle                                   temp. (°C.)                                                                     60     40     20   60   40   20   60  40   20                          ______________________________________                                         E53     783    834    1065 476  1550 7855 29  29   28                          B54             30     76       1265 5440     25   25                          E55      94    187     361 385  1260 5925 29  29   28                          ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                        Example 54: The upperlimit temperature of SCA* was low so that the             measurement at 60° C. was not carried out.                        

EXAMPLES 56-60

The obtained optically active compounds in E3, E4 and E5 in an amount 40 mol % each were respectively mixed with an anti-ferroelectric liquid crystal AF2 (to be referred to as "AF2" hereinafter) of the following formula, to obtain liquid crystal compositions.

Further, E5 in an amount of 30 mol % (Example 59) or 50 mol % (Example 60), was mixed with AF2 to obtain liquid crystal compositions.

    AF2: n--C.sub.9 H.sub.19 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CF.sub.3)(CH.sub.2).sub.5 OC.sub.2 H.sub.5

In the above formula, Ph is a 1,4-phenylene group, Ph(3F) is a 1,4-phenylene group substituted with F on its 3 position (Z=F in formula (2)), and C* is asymmetric carbon.

The above-obtained anti-ferroelectric liquid crystal compositions were phase-identified and measured for response speeds, and Tables 28 and 29 show the results.

EXAMPLE 61

E5 in an amount of 50 mol % was mixed with an anti-ferroelectric liquid crystal AF3 (to be referred to as "AF3" hereinafter) of the following formula, to obtain a liquid crystal composition.

    AF3: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CF.sub.3)(CH.sub.2).sub.5 OC.sub.2 H.sub.5

In the above formula, Ph is a 1,4-phenylene group, Ph(3F) is a 1,4-phenylene group substituted with F on its 3 position (Z=F in formula (2)), and C* is asymmetric carbon.

The above-obtained anti-ferroelectric liquid crystal composition was phase-identified and measured for a response speed, and Tables 28 and 29 show the results.

As shown in Table 29, the compositions are improved particularly in response time I although both the anti-ferroelectric liquid crystals AF2 and AF3 are excellent in response speed.

                                      TABLE 28                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                            Com-  Molar                                 transition temperature (°C.))                                                                              ponent                                                                               ratio                                 __________________________________________________________________________     Liquid                                                                         crystal                                                                        AF2 I (81)                                                                              SC* (79)                                                                               SCA*                                                                               (<-50)                                                                             Cr                                                    AF3 I (90)                                                                              SCA*                                                                               (<-20)                                                                             Cr                                                            E56 I (64)                                                                              SA  (57)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF2/E3 =                                                                             60/40                                 E57 I (62)                                                                              SA  (57)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF2/E4 =                                                                             60/40                                 E58 I (60)                                                                              SA  (52)                                                                               SC* (51)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                                               AF2/E5 =                                                                             60/40                                 E59 I (64)                                                                              SA  (58)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF2/E5 =                                                                             70/30                                 E60 I (58)                                                                              SA  (49)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF2/E5 =                                                                             50/50                                 E61 I (61)                                                                              SA  (50)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF3/E5 =                                                                             50/50                                 __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 29                                                         ______________________________________                                                                        Measured                                                 Response speed I                                                                         Response speed II                                                                          temp. (°C.)                              ______________________________________                                         Liquid crystal AF2                                                                        21          716         30                                          Liquid crystal AF3                                                                        22          303         30                                          Ex. 56     13          651         30                                          Ex. 57     13          1300        30                                          Ex. 58     15          1770        30                                          Ex. 59     15          1285        30                                          Ex. 60     13          651         30                                          Ex. 61     13          296         30                                          ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                  

EXAMPLES 62-66

The optically active compounds E8, E14, E15 and E16 in an amount of 30 mol % each were mixed with a liquid crystal AF3 to obtain anti-ferroelectric liquid crystal compositions (Examples 62 to 65), and 40 mol % of the optically active compound E21 was mixed with a liquid crystal AF3 to obtain an anti-ferroelectric liquid crystal composition (Example 66). These compositions were measured for phase sequences and response times. Tables 30 and 31 show the results.

The liquid crystal AF3 itself is excellent in response time, while the compositions containing AF3 and the optically active compounds of the present invention are further improved in response time I.

                                      TABLE 30                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                    Com-  Molar                                         transition temperature (°C.))                                                                      ponent                                                                               ratio                                         __________________________________________________________________________     Ex. 62                                                                             I  (65)                                                                              SA  (55)                                                                              SCA*                                                                               (<-20)                                                                             Cr                                                                               AF3/E8 =                                                                             70/30                                         Ex. 63                                                                             I  (59)                                                                              SA  (47)                                                                              SCA*                                                                               (<-20)                                                                             Cr                                                                               AF3/E14 =                                                                            70/30                                         Ex. 64                                                                             I  (65)                                                                              SC  (61)                                                                              SCA*                                                                               (<-20)                                                                             Cr                                                                               AF3/E15 =                                                                            70/30                                         Ex. 65                                                                             I  (62)                                                                              SA  (51)                                                                              SCA*                                                                               (<-20)                                                                             Cr                                                                               AF3/E16 =                                                                            70/30                                         Ex. 66                                                                             I  (55)                                                                              SCA*                                                                               (<0)                                                                              Cr        AF3/E21 =                                                                            60/40                                         __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 31                                                         ______________________________________                                                                     Measured                                           Response speed I                                                                               Response speed II                                                                          temp. (°C.)                                 ______________________________________                                         Ex. 62                                                                               16            685         30                                             Ex. 63                                                                               17            639         30                                             Ex. 64                                                                               18            846         30                                             Ex. 65                                                                               16            513         30                                             Ex. 66                                                                               18            312         30                                             ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                  

EXAMPLES 67-70

The optically active compounds E17 to E20 obtained in Examples 17 to 20, in an amount of 30 wt. % each, were respectively mixed with a liquid crystal AF3, and each of the resultant compositions was measured for a phase sequence and a response time. Tables 32 and 33 show the results.

EXAMPLE 71

The optically active compound E11 in an amount of 30 mol % was mixed with an anti-ferroelectric liquid crystal AF4 of the following formula, to obtain a liquid crystal composition, and the composition was measured for a phase sequence and a response time. Tables 32 and 33 show the results.

    AF4: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CF.sub.3)(CH.sub.2).sub.7 OC.sub.2 H.sub.5

In the above formula, Ph is a 1,4-phenylene group, Ph(3F) is a 1,4-phenylene group substituted with F on its 3 position (Z=F in formula (2)), and C* is asymmetric carbon.

REFERENTIAL EXAMPLES 3 AND 4

The optically active compound E11 obtained in Example 11, in an amount of 40 mol % (Referential Example 3) or 50 mol % (Referential Example 4), was mixed with the following anti-ferroelectric liquid crystal AF8, and attempts were made to measure the compositions for a phase sequence and a response time.

    AF8: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph--COO--C*H(CF.sub.3)(CH.sub.2).sub.5 OC.sub.2 H.sub.5

In the above formula, Ph is a 1,4-phenylene group and C* is asymmetric carbon.

Table 33 shows the phase sequences.

The compositions were unmeasurable for a response time since the crystallization proceeded during the application of voltage.

                                      TABLE 32                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                      Com-  Molar                                       transition temperature (°C.))                                                                        ponent                                                                               ratio                                       __________________________________________________________________________     Liquid                                                                              I (90)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                          crystal                                                                        AF3                                                                            E67  I (57)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF3/E17 =                                                                            70/30                                       E68  I (63)                                                                               SA  (49)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                                               AF3/E18 =                                                                            70/30                                       E69  I (59)                                                                               SCA*                                                                               (<-20)                                                                             Cr        AF3/E19 =                                                                            70/30                                       E70  I (62)                                                                               SA  (53)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                                               AF3/E20 =                                                                            70/30                                       Liquid                                                                              I (77)                                                                               SCα*                                                                         (76)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                  crystal                                                                        AF4                                                                            E71  I (58)                                                                               SA  (47)                                                                               SCA*                                                                               (<0)                                                                               Cr                                                                               AF4/E11 =                                                                            70/30                                       Liquid                                                                              I (100)                                                                              SA  (93)                                                                               SCA*                                                                               (43)                                                                               Cr                                                  crystal                                                                        AF8                                                                            Ref. Ex 3                                                                           I (65)                                                                               SA  (42)                                                                               SCA*                                                                               (24)                                                                               Cr                                                                               AF8/E11 =                                                                            60/40                                       Ref. Ex 4                                                                           I (58)                                                                               SA  (33)                                                                               SCA*                                                                               (16)                                                                               Cr                                                                               AF8/E11 =                                                                            50/50                                       __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                      SCα*: chiral smectic a phase                                       

                  TABLE 33                                                         ______________________________________                                                                        Measured                                                 Response speed I                                                                         Response speed II                                                                          temp. (°C.)                              ______________________________________                                         Liquid crystal AF3                                                                        22          303         30                                          E67        16          370         30                                          B68        17          683         30                                          E69        19          498         30                                          E70        18          770         30                                          Liquid crystal AF4                                                                        148         488         30                                          E71        43          783         30                                          ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                  

The liquid crystal AF3 itself is excellent in response time, while the compositions containing AF3 and the optically active compounds of the present invention are further improved in response time I.

The liquid crystal AF4 has a low response time I and has a problem in practical use, while the compositions containing AF4 and the optically active compounds of the present invention are greatly improved in response time.

EXAMPLES 72-75

The optically active compounds E23 and E24 in an amount of 30 mol % each, and the optically active compounds E25 and E26 in an amount of 20 mol % each were respectively mixed with an anti-ferroelectric liquid crystal AF2 to obtain anti-ferroelectric liquid crystal compositions. The compositions were measured for phase sequences and response times, and Tables 34 and 35 show the results.

                                      TABLE 34                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                         Com-  Molar                                    transition temperature (°C.))                                                                           ponent                                                                               ratio                                    __________________________________________________________________________     E72                                                                               I (64)                                                                              SA                                                                               (53)                                                                              SCA*                                                                               (<-20)                                                                             Cr         AF2/E23 =                                                                            70/30                                    E73                                                                               I (67)                                                                              SA                                                                               (57)                                                                              SCA*                                                                               (<-20)                                                                             Cr         AF2/E24 =                                                                            70/30                                    E74                                                                               I (66)                                                                              SA                                                                               (58)                                                                              SC* (53)                                                                               SCA*                                                                               (<-20)                                                                              Cr                                                                               AF2/E25 =                                                                            80/20                                    E75                                                                               I (68)                                                                              SA                                                                               (63)                                                                              SC* (62)                                                                               SCA*                                                                               (<-20)                                                                              Cr                                                                               AF2/E26 =                                                                            80/20                                    __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 35                                                         ______________________________________                                                                     Measured                                           Response speed I                                                                               Response speed II                                                                          temp. (°C.)                                 ______________________________________                                         E72   37             2900       25                                             E73   37             4600       25                                             E74   34            26000       25                                             E75   42            74000       25                                             ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                  

EXAMPLES 76-78

The optically active compound E11 obtained in Example 11 in an amount of 30 mol % was mixed with an anti-ferroelectric liquid crystal AF5, AF6 or AF7 of the following formula, respectively, to obtain anti-ferroelectric liquid crystal compositions. These compositions were measured for phase sequences and response times, and Tables 36 and 37 show the results.

    AF5: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CH.sub.3 C.sub.8 H.sub.17

    AF6: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CH.sub.3 C.sub.4 H.sub.9

    AF7: n--C.sub.8 H.sub.17 --O--Ph--Ph--COO--Ph(3F)--COO--C*H(CH.sub.3 C.sub.6 H.sub.13

In the above formulae, Ph is a 1,4-phenylene group, Ph(3F) is a 1,4-phenylene group substituted with F on its 3 position (Z=F in formula (2)), and C* is asymmetric carbon.

                                      TABLE 36                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                               Com-  Molar                              transition temperature (°C.))  ponent                                                                               ratio                              __________________________________________________________________________     Liquid                                                                             I (131)                                                                             SA                                                                               (114)                                                                             SC* (113)                                                                              SCA*                                                                               (23)                                                                              SIA*                                                                              (<0)                                                                               Cr                                         crystal                                                                        AF5                                                                            Liquid                                                                             I (149)                                                                             SA                                                                               (129)                                                                             SCA*                                                                               (20)                                                                               SIA*                                                                               (-12)                                                                             SX (<-20)                                                                             Cr                                         crystal                                                                        AF6                                                                            Liquid                                                                             I (110)                                                                             SA                                                                               (108)                                                                             SCA*                                                                               (10)                                                                               SX  (<0)                                                                              Cr                                                crystal                                                                        AF7                                                                            E76 I  (96)                                                                             SA                                                                               (63)                                                                              SCA*                                                                               (<-10)                                                                             Cr              AF5/E11 =                                                                            70/30                              E77 I (108)                                                                             SA                                                                               (71)                                                                              SCA*                                                                               (<-10)                                                                             Cr              AF6/E11 =                                                                            70/30                              E78 I  (86)                                                                             SA                                                                               (72)                                                                              SCA*                                                                               (<-10)                                                                             Cr              AF7/E11 =                                                                            70/30                              __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                      SX: Unidentified liquid crystal phase.                                   

                  TABLE 37                                                         ______________________________________                                                  Response Response Tilt    Measured                                             speed I  speed II angle   temp. (°C.)                          ______________________________________                                         Liquid crystal AF5                                                                        351        1430     29    30                                        Liquid crystal AF6                                                                        --*.sup.1  --*.sup.1                                                                               30    30                                        Liquid crystal AF7                                                                        --*.sup.1  --*.sup.1                                                                               37    30                                        E76         26        2645     23    30                                        E77        148        3370     23    30                                        E78         38         867     31    30                                        ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit μsecond.                                                        *.sup.1 Threshold voltage was very high, as high as 20 V/mm or more, so        that the response time was unmeasurable under measurement conditions.    

EXAMPLES 79-85

The two-rings-containing phenyl ester compounds E27 to E33 obtained in Examples 27 to 33, in an amount of 30 mol % in each of E27 and E29 to E33 or 35 mol % in E28, were mixed with a liquid crystal AF2, to obtain anti-ferroelectric liquid crystal compositions. The compositions were measured for phase sequences and response times, and Tables 38 and 39 show the results.

                                      TABLE 38                                     __________________________________________________________________________     Phase sequence (parenthesized values =                                                                          Com-  Molar                                   transition temperature (°C.))                                                                            ponent                                                                               ratio                                   __________________________________________________________________________     Liquid                                                                             I (83)                                                                              SC*                                                                               (77)                                                                              SCA*                                                                               (<-50)                                                                             Cr                                                      crystal                                                                        AF2                                                                            E79 I (85)                                                                              SA (71)                                                                              SC* (65)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                                               AF2/E27 =                                                                            70/30                                   E80 I (84)                                                                              SA (73)                                                                              SC* (65)                                                                               SCA*                                                                               (<-20)                                                                             Cr                                                                               AF2/E28 =                                                                            65/35                                   E81 I (79)                                                                              SA (59)                                                                              SCA*                                                                               (<-20)                                                                             Cr        AF2/E29 =                                                                            70/30                                   E82 I (81)                                                                              SA (62)                                                                              SCA*                                                                               (<-20)                                                                             Cr        AF2/E30 =                                                                            70/30                                   B83 I (82)                                                                              SA (70)                                                                              SCA*                                                                               (<-20)                                                                             Cr        AF2/E31 =                                                                            70/30                                   E84 I (82)                                                                              SA (72)                                                                              SCA*                                                                               (<-20)                                                                             Cr        AF2/E32 =                                                                            70/30                                   E85 I (86)                                                                              SA (70)                                                                              SCA*                                                                               (<-20)                                                                             Cr        AF2/E33 =                                                                            70/30                                   __________________________________________________________________________      Notes)                                                                         For abbreviations, see notes to Table 18.                                

                  TABLE 39                                                         ______________________________________                                                    Response Response Measured                                                     speed I  speed II temp. (°C.)                                ______________________________________                                         Liquid crystal AF2                                                                          79         2020     10                                            E79          64         8500     10                                            E80          61         6600     10                                            E81          64         9600     10                                            E82          67         8100     10                                            E83          51         1200     10                                            E84          72         7500     10                                            E85          71         3300     10                                            ______________________________________                                          Notes)                                                                         Response speed I: speed from antiferroelectric state to ferroelectric          state, unit μsecond.                                                        Response speed II: speed from ferroelectric state to antiferroelectric         state, unit second.                                                      

As is clearly shown in Tables 38 and 39, the liquid crystal AF2 has no smectic A phase, while there are obtained compositions having a smectic A phase by incorporating the two-rings-containing phenyl ester compounds. Further, the compositions retain an anti-ferroelectric phase in a broad temperature range and are improved in response time I at 10° C. 

What is claimed is:
 1. An anti-ferroelectric liquid crystal composition containingat least one two-ringed phenyl ester compound of the following general formula (1) ##STR14## wherein R¹ is a linear alkyl group having 5 to 12 carbon atoms, R² is a linear alkyl group having 1 to 15 carbon atoms, X¹ and X² are both hydrogen atoms or one of X¹ and X² is a fluorine atom and the other is a hydrogen atom, Y¹ and Y² are both hydrogen atoms or one of Y¹ and Y² is a fluorine atom and the other is a hydrogen atom, A¹ is --CH₃ or --CF₃, provided that when A¹ is --CH₃, p is 0, and that when A¹ is --CF₃, p is 1 and q is an integer of 5 to 8; and either an anti-ferroelectric liquid crystal compound or a mixture of anti-ferroelectric liquid crystal compounds.
 2. The anti-ferroelectric liquid crystal composition of claim 1, wherein the anti-ferroelectric liquid crystal composition at least has an anti-ferroelectric phase in a temperature range of from 0° to 40° C.
 3. The anti-ferroelectric liquid crystal composition of claim 1, wherein the anti-ferroelectric liquid crystal composition has at least a smectic A phase on a side of temperatures higher than a temperature at which an anti-ferroelectric phase is exhibited.
 4. The anti-ferroelectric liquid crystal composition of claim 1, wherein the anti-ferroelectric liquid crystal compound has, or the anti-ferroelectric liquid crystal compounds have, the following general formula (2), ##STR15## wherein R³ is a linear alkyl group having 4 to 12 carbon atoms, R⁴ is a linear alkyl group having 1 to 12 carbon atom, Z is a hydrogen atom or a fluorine atom, A² is a --CH₃ or --CF₃, s is 0 or 1, t is an integer of 5 to 8, and C* is an asymmetric carbon, provided that when A² is --CH₃ and s is 0, R⁴ is a linear alkyl group having 3 to 10 carbon atoms, that when A² is --CF₃ and s is 0, R⁴ is a linear alkyl group having 4 to 8 carbon atoms, and that when A² is --CF₃ and s is 1, t is an integer of 5 to 8 and R⁴ is a linear alkyl group having 1 to 6 carbon atoms.
 5. The anti-ferroelectric liquid crystal composition of claim 4, wherein the anti-ferroelectric liquid crystal compound has, or the anti-ferroelectric liquid crystal compounds have, the general formula (2) in which R³ is a linear alkyl group having 6 to 10 carbon atoms.
 6. The anti-ferroelectric liquid crystal composition of claim 4, wherein the anti-ferroelectric liquid crystal compound has, or the anti-ferroelectric liquid crystal compounds have, the general formula (2) in which A² is --CH₃, s is 0 and R⁴ is a linear alkyl group having 4, 6 or 8 carbon atoms.
 7. The anti-ferroelectric liquid crystal composition of claim 4, wherein the anti-ferroelectric liquid crystal compound has, or the anti-ferroelectric liquid crystal compounds have, the general formula (2) in which A² is --CF₃, s is 0 and R⁴ is a linear alkyl group having 6 carbon atoms.
 8. The anti-ferroelectric liquid crystal composition of claim 4, wherein the anti-ferroelectric liquid crystal compound has, or the anti-ferroelectric liquid crystal compounds have, the general formula (2) in which A² is --CF₃, s is 1, t is an integer of 5 or 7 and R⁴ is ethyl.
 9. The anti-ferroelectric liquid crystal composition of claim 4, wherein the anti-ferroelectric liquid crystal composition at least has an anti-ferroelectric phase in a temperature range of from 0° to 40° C. and has at least a smectic A phase on a side of temperatures higher than a temperature at which the anti-ferroelectric phase is exhibited.
 10. A simple matrix liquid crystal display device characterized in that the anti-ferroelectric liquid crystal composition of claim 1 is held between two substrates, one substrate having scanning electrodes disposed in a matrix form and the other substrate having signal electrodes disposed in a matrix form.
 11. The simple matrix liquid crystal display device of claim 10, wherein actuation of the simple matrix liquid crystal display device by voltage can be performed by switching between one anti-ferroelectric state and two ferroelectric states. 